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Benzene cluster cations were revisited as a sensitive and selective reagention for the chemical ionization of dimethyl sulfide (DMS) and a select groupof volatile organic compounds (VOCs). Laboratory characterization wasperformed using both a new set of compounds (i.e., DMS, β-caryophyllene)as well as previously studied VOCs (i.e., isoprene, α-pinene). Usinga field deployable chemical-ionization time-of-flight mass spectrometer(CI-ToFMS), benzene cluster cations demonstrated high sensitivity(> 1 ncps ppt−1) to DMS, isoprene, and α-pinenestandards. Parallel measurements conducted using a chemical-ionizationquadrupole mass spectrometer, with a much weaker electric field,demonstrated that ion–molecule reactions likely proceed through acombination of ligand-switching and direct charge transfer mechanisms.Laboratory tests suggest that benzene cluster cations may be suitable forthe selective ionization of sesquiterpenes, where minimal fragmentation(< 25 %) was observed for the detection of β-caryophyllene, abicyclic sesquiterpene. The in-field stability of benzene cluster cationsusing CI-ToFMS was examined in the marine boundary layer during the HighWind Gas Exchange Study (HiWinGS). The use of benzene cluster cationchemistry for the selective detection of DMS was validated against anatmospheric pressure ionization mass spectrometer, where measurements fromthe two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions

Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds